Phosphor paste compositions and phosphor coatings obtained therefrom

ABSTRACT

A phosphor paste composition is disclosed, which uses as an organic binder an acrylic polymer obtained by copolymerizing an alkyl methacrylate as a principal component with a specific amount of at least one monomer selected from unsaturated carboxylic acids and hydroxyalkyl (meth)acrylates. Also disclosed is a phosphor paste composition making use of a phosphor having a volume average particle size in a range of 1-7 μm, with particles having a particle size of 1-9 μm accounting for at least 60 wt.%. These phosphor paste compositions have excellent firing characteristics and provide phosphor coatings excellent in both light-emitting characteristics and resolution.

This is a division of application Ser. No. 07/323,794, filed on Mar. 15,1989 now U.S. Pat. No. 5,132,045.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to phosphor pastes for printing capable ofproviding a uniform and high-resolution phosphor coating which isrequired for the formation of a fluorescent screen of a cathode ray tube(hereinafter abbreviated as "CRT").

2. Description of the Prior Art

A CRT typified by a TV Braun tube is a display device in which electronbeams emitted from an electron gun are projected on a phosphor coatingto excite the phosphor to produce luminous spots in the form of apattern. A variety of visual equipment making use of a high electronictechnique has been developed. Their display devices range from colordisplay devices to monochrome display devices. These display devicesalso vary widely in size from large to very small. It is the phosphorcoating formed on a glass plate of a CRT that governs the performance ofthe CRT which makes up the heart of such visual equipment. As productionprocesses for the phosphor coating, there have been known, for example,slurry processes, settling processes, electrophoretic depositionprocesses and vacuum evaporation processes for a monochrome CRT. Amongthese, the settling process making use of a phosphor, and an inorganicbinder is generally used to form a phosphor coating for ahigh-resolution monitor CRT. However, the surface of the phosphorcoating obtained by this process is excessively rough. This process cantherefore hardly provide a phosphor coating of uniform thickness andhigh resolution. On the other hand, the phosphor coating of a color CRTcontains three phosphors of red, green and blue colors arranged in theform of dots or stripes. Photo-curing processes using a shadow mask haveconventionally been used for its formation. Use of a shadow mask with afine pattern formed therein is however indispensable for the formationof the fluorescent screen of a color CRT by this process. A shadow maskof higher accuracy is required as the CRT becomes smaller in size or aCRT having a screen of higher resolution is desired. In addition, it isalso necessary to develop a high-performance phosphor slurry usable forthe formation of such a phosphor coating. The formation of a fluorescentscreen by the photo-curing process using a shadow mask is accompanied byproblems in that there is a higher initial cost, time- andlabor-consuming recovery of extra phosphor resulting in the course offormation of the fluorescent screen is necessary and the phosphor issubstantially lost. Accordingly, a printing process has recently beendeveloped for the formation of a phosphor coating having a uniformthickness and little roughness on the surface of the phosphor coatingand hence suited for a high-resolution CRT. According to this process, aCRT panel (front glass plate) is printed either directly or indirectlywith a paste composed of a phosphor, an organic resin binder and asolvent and the binder resin component in the paste is thereafter burntaway to form a fluorescent screen. This process is industriallyadvantageous, because compared to the conventional processes for theformation of a phosphor coating the initial cost is lower, the loss ofthe phosphor is smaller and the material cost can hence be reduced, andthe productivity is higher. As known phosphor pastes usable for thisprocess, reference may be made to Japanese Patent Publication No.23231/1986 and Japanese Patent Laid-Open No. 213778/1984.

As resins useful in these phosphor pastes, there are cellulose resinsand vinyl alcohol resins. They however all require a high firingtemperature and without exception also leave carbon as a residue. Thephysical properties of a phosphor coating formed from such a phosphorpaste are thus poor, in particular, the lifetime of the resultant CRT isshort. In addition, black spots are formed on the surface of thephosphor coating when the CRT is rendered luminous, so that theresolution of the CRT is lowered and the picture quality isdeteriorated. In particular, the use of a resin of natural origin, e.g.,cellulose as a binder, tends to result in the mixing of unexpected ionicimpurities which may impair the characteristics of the phosphor or inthe remaining of impurities which may deteriorate the burning-awayproperty, since it is difficult to purify such a resin. It is thereforeimpossible to form a phosphor coating of high resolution from a phosphorpaste which contains such a resin as a binder. As phosphor pastes saidto have improved this problem, phosphor pastes making use of a syntheticresin of good burning-away property, for example, an alkyd resin orphenol resin have been proposed. These resins are however oil-solubleand have insufficient compatibility with a phosphor which is basicallyhydrophilic, whereby the dispersion of the phosphor would be poor inpastes to be formed. In other words, a coating formed by the printingprocess from such a phosphor paste is barely imparted with highresolution because it contains pinholes, the coating has poor levelling,and the phosphor is not coated evenly, therefore the uniformlight-emitting property is poor.

Developed as phosphor pastes free of these inconvenience are those addedwith a compound which contain highly-ionic functional groups havingcompatibility with the phosphor, for example, phosphoric groups ornitrogen-containing functional groups. These phosphor pastes howeverhave poor firing characteristics, thereby making it difficult to obtainfrom them a phosphor coating of high resolution and good picturequality.

For the production of color fluorescent screens, it is necessary toprint a phosphor in a pattern such as stripes or dots. It is howeverdifficult to print such a pattern in a desired size and with goodaccuracy whichever conventional phosphor paste is used. The primaryreasons for this problem are that the phosphor pastes have insufficientthixotropy and the stripe or dot pattern once formed is allowed to flowto result in deformation.

SUMMARY OF THE INVENTION

The present inventors conducted research with a view to developing aphosphor paste free of the inconvenience described above. As a result,it has been found that the object can be achieved by improving thecharacteristics of particles of a phosphor pigment, which forms thephosphor paste, and by using a binder resin having excellentcompatibility with the phosphor pigment and superb burning-awayproperty. The above finding has led to the completion of this invention.

An object of this invention is therefore to provide a phosphor pastecomposition having excellent firing characteristics and suitable for usein the formation of a phosphor coating for a CRT, said coating beingexcellent in resolution and light-emitting characteristics.

Another object of this invention is to provide a phosphor coating for ahigh-resolution CRT, said coating having little roughness, beingsubstantially free of pinholes and excellent in light-emittingcharacteristics.

In one aspect of this invention, there is thus provided a phosphor pastecomposition comprising:

(A) 100 parts by weight of an acrylic polymer obtained by copolymerizing(a) 52-99.9 wt.% of an alkyl methacrylate, (b) at least 0.1 wt.% of atleast one monomer selected from unsaturated carboxylic acids andhydroxyalkyl (meth)acrylates with the proviso that the total proportionof the one or more unsaturated carboxylic acids is not greater than 8wt.% and that the total proportion of the one or more hydroxylalkyl(meth)acrylates if contained is not greater than 40 wt.%, and (c) 0-20wt.% of another vinyl monomer copolymerizable with the above monomers;

(B) 250-2000 parts by weight of a phosphor; and

(C) a solvent; said composition having a viscosity of 5,000-10,000 cpsat 25° C.

In another aspect of this invention, there is also provided a phosphorpaste composition comprising a phosphor with a layer of an activator,said phosphor having a volume average particle size in a range of 1-7 μmwith particles having a particle size of 1-9 μm accounting for at least60 wt.%, an organic resin binder and an organic solvent, saidcomposition having a viscosity of 5,000-200,000 cps at 25° C.

In a further aspect of this invention, there is also provided a phosphorcoating formed by printing a pattern with a phosphor paste compositioncontaining a phosphor pigment with a layer of an activator, saidphosphor having a volume average particle size in a range of 1-7 μm,with particles having a particle size of 1-9 μm accounting for at least60 wt.%, and then firing the phosphor paste composition.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

An acrylic polymer is preferred as the organic resin binder for thephosphor paste composition according to this invention, although aconventionally-known resin such as an alkyd resin, ethylcellulose orphenol resin can also be used. As a particularly preferable acrylicpolymer, may be mentioned an acrylic polymer (A) obtained bycopolymerizing (a) 52-99.9 wt.% of an alkyl methacrylate, (b) at least0.1 wt.% of at least one monomer selected from unsaturated carboxylicacids and hydroxyalkyl (meth)acrylates with the proviso that the totalproportion of the one or more unsaturated carboxylic acids if containedis not greater than 8 wt.% and that the total proportion of the one ormore hydroxylalkyl (meth)acrylates if contained is not greater than 40wt.%, and (c) 0-20 wt.% of another vinyl monomer copolymerizable withthe above monomer. It is essential that 52-99.9 wt.% of the alkylmethacrylate be copolymerized in the acrylic polymer (A). If theproportion of the alkyl methacrylate is smaller than 52 wt.%, theacrylic polymer (A) has insufficient burning-away property. On the otherhand, proportions greater than 99.9 wt.% lead to an acrylic polymerhaving insufficient compatibility with the phosphor, thereby failing toprovide any phosphor paste consistent with the objects of thisinvention. Specific examples of the alkyl methacrylate include C₁₋₈-alkyl methacrylates such as methyl methacrylate, ethyl methacrylate,n-butyl methacrylate and isobutyl methacrylate. One or more of thesemonomers may be chosen as desired in view of their firing conditionssuch as burning starting temperatures, complete burning-awaytemperatures, volume reducing rates upon firing, and the desired degreeof improvement to the thixotropy of a phosphor paste containing theacrylic polymer. However, it is particularly preferred to use ethylmethacrylate or isobutyl methacrylate as the principal alkylmethacrylate.

It is necessary for the acrylic polymer (A)used in this invention thatat least one compound selected from unsaturated carboxylic acids andhydroxylalkyl (meth)acrylates be copolymerized in a proportion of atleast 0.1 wt.%. An acrylic polymer containing at least 0.1 wt.% of suchpolar-group-containing monomer units has extremely good compatibilitywith a phosphor, thereby making it possible to prepare a paste in whichthe phosphor is stably dispersed.

To obtain the acrylic polymer (A), one or more unsaturated carboxylicacids are preferably copolymerized up to 8 wt.% in total. If an acrylicpolymer obtained by copolymerizing one or more unsaturated carboxylicacids in a total proportion greater than 8 wt.% is used as a binderresin to prepare a paste, the phosphor is prone to aggregation in thepaste, and the burning-away property of the acrylic polymer tends todeteriorate. It is hence not preferable to use one or more unsaturatedcarboxylic acids in such a large total proportion. The preferable totalproportion of one or more unsaturated carboxylic acids to becopolymerized is at least 0.1 wt.%, more preferably 0.3-5 wt.%. Asspecific examples of the unsaturated carboxylic acids, may be mentionedacrylic acid, methacrylic acid, itaconic acid, phthalic acid and maleicacid.

To obtain the acrylic polymer (A), one or more hydroxyalkyl(meth)acrylates are preferably copolymerized up to 40 wt.% in total. Anacrylic polymer obtained by copolymerizing one or more hydroxyalkyl(meth)acrylates in a total proportion greater than 40 wt.% hasdeteriorated burning-away property and is hence not preferred. Aspreferable specific examples of the hydroxyalkyl (meth)acrylates, may bementioned those containing an alkyl group having 1-4 carbon atoms suchas hydroxyethyl (meth)acrylates, hydroxypropyl (meth)acrylates andhydroxybutyl (meth)acrylates.

It is necessary for the acrylic copolymer (A) employed in this inventionthat at least one of unsaturated carboxylic acids and hydroxyalkyl(meth)-acrylates be copolymerized in a proportion of at least 0.1 wt.%,preferably at last 0.3 wt.%. An acrylic polymer in which thecopolymerized proportion of at least one of these components is smallerthan 0.1 wt.% has insufficient compatibility with the phosphor. Use ofsuch an acrylic polymer results in failure to provide a phosphor pastehaving properties intended to be obtained in this invention.

In the acrylic polymer (A) useful in the practice of this invention, itis also possible to copolymerize not more than 20 wt.% of another vinylmonomer copolymerizable with the monomers described above. Specificexamples of the copolymerizable vinyl monomer include alkyl acrylatessuch as ethyl acrylate, propyl acrylate and butyl acrylate as well asvinyl acetate, vinyl ethoxyacetate, vinyl propionate, methyl vinylether, ethyl vinyl ether, isopropyl vinyl ether, n-propyl vinyl ether,methyl vinyl ketone, ethyl vinyl ketone, n-propyl vinyl ketone,isopropyl vinyl ketone, γ-methacryloxypropyltrimethoxysilane,γ-methaoryloxypropyltris(β-methoxyethoxy)silane,methacryloxymethyltrimethoxysilane,3-methacryloxypropylmethyldimethoxysilane, styrene, o-methylstyrene,m-methylstyrene, p-methylstyrene, o-vinylbenzoic acid, p-vinylbenzoicacid, 2,4-dimethylstyrene, 3,4-dimethylstyrene and 3,5-dimethylstyrene.They may be used either singly or in combination to the extent of notcausing any problem with respect to the burning-away property of theacrylic polymer.

It is also possible to copolymerize a further polyfunctionalcrosslinkable monomer, e.g., divinylbenzene or ethylene glycoldi(meth)acrylate, to the extent of not impairing the burning-awayproperty of the acrylic polymer.

In the present invention, the phosphor is added in a proportion of250-2,000 parts by weight per 100 parts by weight of the acrylic polymer(A). Proportions of the phosphor smaller than 250 parts by weight per100 parts by weight of the acrylic polymer (A) are too small to providea phosphor coating having uniform light-emitting characteristics. On theother hand, a phosphor paste containing the phosphor in a proportiongreater than 2,000 parts by weight can form only a phosphor coatinghaving low levelling property. When this phosphor paste is applied bythe screen printing process, the resulting coating contains pinholes orsurface roughness, thereby failing to provide a phosphor coating havinguniform light-emitting characteristics.

Preferably, the phosphor paste composition according to this inventionhas a viscosity of about 5,000-200,000 cps at 25° C. It is thuspreferable to add an organic solvent having a boiling point of at least150° C to the phosphor paste. If an organic solvent to be added to thephosphor paste has a boiling point lower than 150° C, the viscosity ofthe resulting phosphor paste composition varies upon printing, therebyfailing to form a phosphor coating having uniform light-emittingcharacteristics.

Specific examples of the solvent include diethylene glycol monoethylether acetate, diethylene glycol monobutyl ether acetate,2,2,4-trimethyl-1,3-pentadiol monoisobutyrate, isophorone and3-methoxybutyl acetate.

A coating formed from a phosphor paste whose viscosity is lower than5,000 cps tends to develop bleeding or the like at the edges, so thatthe reproducibility of a stripe or dot pattern is inferior. On the otherhand, a phosphor paste whose viscosity is higher than 200,000 cps hasinsufficient coatability. A coating formed from such a phosphor pastethus has surface roughness, thereby failing to exhibit uniformlight-emitting characteristics.

In addition, the phosphor paste composition of this invention may alsobe added with various additives such as conventional plasticizers,dispersion stabilizers, levelling agents and thixotropic agents, as longas their proportions are limited within the ranges of not impairing theproperties of the phosphor paste composition.

Preferably, the phosphor employed in this invention is almost whollysurface-coated with an activator and has a volume average particle sizein a range of 1-7 μm, with particles having a particle size of 1-9 μmaccounting for at least 60 wt.%. A phosphor containing particles whichhave some surface areas not coated with the activator is not preferable,because the light-emitting characteristics are deteriorated.

Phosphor particles employed for the formation of a phosphor screen of amonochrome cathode ray tube preferably have a volume average particlesize of 1-4 μm. It is difficult to produce a phosphor having a volumeaverage particle size smaller than 1 μm. Such a fine phosphor isexpensive and, when mixed with a binder and a solvent into a phosphorpaste, the phosphor particles aggregate again in the phosphor paste. Itis therefore difficult to form, from this phosphor paste, a phosphorcoating having high luminance and uniform light-emittingcharacteristics. To avoid formation of pinholes in a phosphor coatingfor a monochrome CRT and to impart good surface smoothness to thecoating so that the coating may have good characteristics, it ispreferable to control the volume average particle size to 1-4 μm.

In a monochrome phosphor, the content of particles having a particlesize of 1-6 μm are at least 60 wt.%, preferably at least 80 wt.%. If thecontent of phosphor particles having a particle size of 1-6 μm is lowerthan 60 wt.% in a phosphor pigment, the resulting phosphor paste canonly form a phosphor coating containing pinholes and having insufficientsmoothness or a phosphor coating with phosphor particles aggregated asgranules, thereby making it difficult to provide a phosphor coatinghaving uniform light-emitting characteristics.

Phosphor particles employed for the formation of a phosphor screen of acolor cathode ray tube preferably have a volume average particle size of2-7 μm. It is difficult to produce a color phosphor having a volumeaverage particle size smaller than 2 μm. Such a fine color phosphor issusceptible to a reduction in luminous efficiency so that its lifetimeis short. Further, the luminous efficiency of the phosphor of each ofthe red, green and blue colors varies depending on the particle size. Asthe particle size becomes smaller, the differences in luminousefficiency among phosphor particles become greater, thereby failing toprovide a color phosphor coating having uniform light-emittingcharacteristics. On the other hand, a phosphor paste making use ofphosphor particles whose volume average particle size is greater than 7μm has difficulty in forming a fluorescent screen of good patternaccuracy by the printing process. In addition, the resulting coating hasa rough surface. In a mixture of color phosphor particles, theproportion of phosphor particles having a particle size of 1-9 μm shouldaccount for at least 60%, preferably at least 80%. A CRT coating formedfrom color phosphor particles whose particle size distribution isbroader than that described above is not preferable because of pinholes,insufficient smoothness and/or aggregated phosphor particles (i.e.,granules).

No particular limitations are imposed on the phosphor and activator tobe used in this invention. A suitable phosphor and activator can bechosen from those well known in the art, as desired depending on the enduse, for example, whether the end use is for a monochrome CRT or for acolor CRT.

This invention will hereinafter be described in detail by the followingexamples, in which all designations of "part or parts" and "%" indicatepart or parts by weight and wt.%, respectively.

EXAMPLE 1

In 180 parts of diethylene glycol monoethyl ether acetate, 98 parts ofethyl methacrylate (EMA), 2 parts of methacrylic acid (MAA) and 2.0parts of azobisisobutyronitrile were reacted at 80° C. for 10 hours. Thesolid content of the reaction mixture was 35%. An acrylic polymer thusobtained had a volume average molecular weight of 170,000. Dispersed in100 solid parts of the thus-obtained acrylic polymer were 344.8 parts offine monochrome phosphor powder "P-45", which was yttrium oxysulfide (Y₂O₂ S) coated with terbium as an activator, having a volume averageparticle size of 3.0 μm and containing 5% of phosphor particles greaterthan 6 μm. The resultant mixture was kneaded and its viscosity wasadjusted with diethylene glycol monoethyl ether acetate to 15,000 cps asmeasured at 25° C. by an EHD-type viscometer manufactured by Tokyo KeikiCo., Ltd., thereby obtaining a phosphor paste composition.

The composition obtained as described above was then coated to athickness of 20 μm on a glass plate by the screen printing process,followed by drying and firing. The surface of a phosphor coating thusobtained was investigated. The state of the surface of the phosphorcoating was evaluated by an optical microscope of 50-400 magnifications,using both transmitted light and reflected light. As a result, thesurface of the resultant phosphor coating was found to contain nopinholes, to have high covering power and to present a smooth surface.

EXAMPLES 2 AND 3 & COMPARATIVE EXAMPLES 1 AND 2

Phosphor paste compositions were separately prepared in a similar manneras in Example 1 except that acrylic polymers were produced by changingthe proportions of the monomer components as shown in Table 1. Theresults are also shown in Table 1.

                  TABLE 1                                                         ______________________________________                                               Monomer   Evaluated property                                                  component Pinholes           Firing                                           EMA   MAA     in               charac-                                        (%)   (%)     coating  Smoothness                                                                            teristics                               ______________________________________                                        Ex. 1    98      2.0     ⊚                                                                     ⊚                                                                      ◯                         Ex. 2    99.5    0.5     ⊚                                                                     ◯                                                                         ◯                         Ex. 3    95      5.0     ⊚                                                                     ⊚                                                                      ◯                         Comp. Ex. 1                                                                            100     0       X      X       ◯                         Comp. Ex. 2                                                                            90      10      X      X       Δ                               ______________________________________                                    

The evaluation was conducted in accordance with the following standards.

Pinholes in Coating

Each phosphor paste composition was printed, dried and fired. Thesurface of a phosphor coating thus formed was investigated by theoptical microscope of 50-400 magnifications, using transmitted light,whereby it was determined whether the surface contained pinholes or not.

⊚: No pinhole was observed at all.

◯: Substantially no pinholes were observed.

Δ: Some pinholes were observed.

X: Relatively many pinholes were observed.

Smoothness

Each phosphor paste composition was printed, dried and fired. Thesurface of a phosphor coating thus formed was evaluated by the opticalmicroscope of 50-400 magnifications, using reflected light.

⊚: Very little roughness without any trace of the screen mesh.

◯: Only small roughness without any trace of the screen mesh.

Δ: Fairly large roughness.

X: Very large roughness with trace of the screen mesh.

Firing characteristics

Heating rate: 15° C./min.

Sample quantity: 10 mg.

Firing temperature range: from room temperature to 400° C.

◯: No residue.

X: Residue was left over.

As is apparent from the above results, the phosphor coating containedpinholes and had poor smoothness in Comparative Example 1 in whichmethacrylic acid was not included at all. It is also appreciated fromComparative Example 2 that the use of methacrylic acid in a proportionas much as 10% led not only to the formation of pinholes in the coatingand the reduced smoothness but also to the reduced firingcharacteristics.

EXAMPLES 4-6 & COMPARATIVE EXAMPLE 3 AND 4

Phosphor paste compositions were separately prepared by changing, asshown in Table 2, the proportions of an acrylic polymer, which had beenobtained in a similar manner as in Example 1 except for the use ofisobutyl methacrylate instead of EMA, and a phosphor of the same kind asthat employed in Example 1. The state of each printed coating wasevaluated in a similar manner as in Example 1.

                  TABLE 2                                                         ______________________________________                                        Paste                                                                         composition (parts)                                                           Acrylic               Pinholes        Firing                                  polymer (A)           in       smooth-                                                                              charac-                                 (solids)     Phosphor coating  ness   teristics                               ______________________________________                                        Comp. 100        200      X      ◯                                                                        ◯                         Ex. 3                                                                         Ex. 4 100        280      Δ-◯                                                                ◯                                                                        ◯                         Ex. 5 100        340      ⊚                                                                     ⊚                                                                     ◯                         Ex. 6 100        1250     Δ-◯                                                                Δ-◯                                                                ◯                         Comp. 100        2500     X      X      ◯                         Ex. 4                                                                         ______________________________________                                    

EXAMPLES 7-9 & COMPARATIVE EXAMPLES 5 AND 6

Printed coatings were obtained respectively by changing the viscosity ofa phosphor paste composition as shown in Table 3, which were obtained ina similar manner as in Example 1 except that 99.5 parts of isobutylmethacrylate, 0.5 part of MAA and diethylene glycol monobutyl etheracetate were used instead of 98 parts of EMA, 2 parts of MAA anddiethylene glycol monoethyl ether acetate. The state of each of theprinted coatings was then evaluated in a similar manner as in Example 1.

                  TABLE 3                                                         ______________________________________                                                Viscosity                                                                            Pinholes           Bleeding*                                           of paste                                                                             in        Smooth-  of                                                  (cps)  coating   ness     coating                                     ______________________________________                                        Comp. Ex. 5                                                                              3000    X         ◯                                                                        X                                         Ex. 7      7500    ◯-Δ                                                                   ⊚                                                                     Δ-◯                     Ex. 8     15000    ⊚                                                                        ⊚                                                                     ◯                             Ex. 9     30000    Δ   Δ                                                                              ◯                             Comp. Ex. 5                                                                             220000   X         X      ◯                             ______________________________________                                         *Bleeding of coating: Protrusions from edges of printed coating.              X: 20 μm or greater.                                                       Δ: Smaller than 20 μm but not smaller than 15 μm.                 ◯: Smaller than 15 μm.                                    

As is understood from Table 3, when the paste viscosity was too low asin Comparative Example 5, the surface of the resultant phosphor coatinghad abnormal luminance and resolution at a peripheral part thereof dueto the bleeding of the coating and moreover, pinholes were formedbecause only portions corresponding to the binder resin were subjectedto levelling. On the other hand, when the paste viscosity was too highas in Comparative Example 6, the resultant coating had poor smoothnessand contained pinholes.

EXAMPLES 10 AND 11 & COMPARATIVE EXAMPLE 7

Coatings were formed separately in exactly the same manner as in Example1 except that acrylic monomers obtained by polymerizing monomercomponents in the proportions shown in Table 4 were used respectively.The state of each of the coating was evaluated in a similar manner as inExample 1.

                                      TABLE 4                                     __________________________________________________________________________                   Further                Pinholes                                       EMA MAA copolymerizable                                                                        Firing        in                                             (%) (%) vinyl monomer                                                                          characteristics                                                                       Smoothness                                                                          coating                                 __________________________________________________________________________    Ex. 2  99.5                                                                              0.5 --       ◯                                                                         ◯                                                                       ◯                           Ex. 10 98.5                                                                              0.5 γ-methacryloxy-                                                                  ◯                                                                         ◯                                                                       ◯                                          propyltrimethoxy-                                                             silane (1%)                                                    Ex. 11 94.5                                                                              0.5 Styrene (5%)                                                                           ◯-Δ                                                                 ◯                                                                       ◯                           Comp. Ex. 7                                                                          69.5                                                                              0.5 Styrene (30%)                                                                          X       ◯-Δ                                                               ◯                           __________________________________________________________________________

EXAMPLE 12

In 2,2,4-trimethyl-1,3-pentadiol monoisobutyrate, 99.5 parts of isobutylmethacrylate, 0.5 part of methacrylic acid and 1.5 parts of benzoylperoxide were reacted at 80° C. for 10 hours. An acrylic polymer thusobtained had a volume average molecular weight of 150,000. Dispersed in100 solid parts of the thus-obtained acrylic polymer were 400 parts offine color phosphor powder "P-22", which was composed of red phosphorpowder of yttrium oxysulfide (Y₂ O₂ S) coated with europium as anactivator, green phosphor powder of zinc sulfide (ZnS) coated withcopper as an activator and blue phosphor powder of zinc sulfide (AnS)coated with silver. The volume average particle size of the colorphosphor powder was 4.5 μm, and phosphor particles greater than 9 μmaccounted for 9% of the whole color phosphor powder. The resultantmixture was kneaded and its viscosity was adjusted with2,2,4-trimethyl-1,3-pentadiol isobutyrate to 50,000 cps as measured at25° C., thereby obtaining a phosphor paste composition. The compositionthus obtained was then coated in the form of stripes, which had apattern width of 150 μm and a thickness of 20 μm, on a glass plate bythe screen printing process, followed by drying and firing. The surfaceof a phosphor coating thus obtained was investigated. The state of thesurface of the phosphor coating was evaluated by the optical microscopeof 50-400 magnifications to evaluate the pattern accuracy the surfacestate. As a result, the surface of the resultant phosphor coating wasfound to have a pattern accuracy of ±10 μm and to present a smoothsurface having no rough area.

EXAMPLE 13

In 180 parts of diethylene glycol monoethyl ether acetate, 90 parts ofisobutyl methacrylate (iBMA), 10 parts of 2-hydroxyethyl methacrylate(HEMA) and 3.0 parts of azobisisobutyronitrile were reacted at 80° C.for 10 hours. An acrylic polymer thus obtained had a weight averagemolecular weight of 200,000. Dispersed in 100 solid parts of the acrylicpolymer were 400 parts of a color phosphor (P-22) of the same kind asthat employed in Example 12. The resultant mixture was kneaded and itsviscosity was adjusted with diethylene glycol monoethyl ether acetate to30,000 cps as measured at 25° C. by the EHD-type viscometer manufacturedby Tokyo Keiki Co., Ltd., thereby obtaining a phosphor pastecomposition.

The composition obtained as described above was then coated in the formof stripes, which had a pattern width of 150 μm and a thickness of 20μm, on a glass plate by the screen printing process, followed by dryingand firing. The surface of a phosphor coating thus obtained wasevaluated. The surface of the phosphor coating was evaluated by theoptical microscope of 50-400 magnifications to evaluate the patternaccuracy and surface state. As a result, the surface of the resultantphosphor coating was found to have a pattern accuracy of ±10 μm and topresent a smooth surface having no rough area.

EXAMPLES 14 AND 15 & COMPARATIVE EXAMPLES 8-10

Printed coatings were formed separately in a similar manner as inExample 13 except for the use of acrylic polymers obtained in accordancewith their respective monomer compositions shown in Table 5. The stateof each of the printed coatings was then evaluated in a similar manneras in Example 13.

                  TABLE 5                                                         ______________________________________                                                                             Firing                                                      150 μm         charac-                                  Monomer composition                                                                              pattern  Smooth-  teris-                                   iBMA      HEMA     MAA     accuracy                                                                             ness   tics                                 ______________________________________                                        Comp. 100      0       0     Δ-X                                                                            X      ◯                      Ex. 8                                                                         Ex. 13                                                                              90      10       0     ◯                                                                        ◯                                                                        ◯                      Ex. 14                                                                              89      10       1     ◯                                                                        ⊚                                                                     ◯                      Ex. 15                                                                              65      35       0     ◯                                                                        ⊚                                                                     ◯                      Comp. 55      45       0     ◯                                                                        ◯-Δ                                                                X                                  Ex. 9                                                                         Comp. 60       8       32    Δ-X                                                                            X      X                                  Ex. 10                                                                        ______________________________________                                    

150 μm Pattern accuracy

A pattern of 150 μm wide stripes was printed through a #300 mesh screen.The widths of stripes thus coated were measured by the opticalmicroscope of 50-400 magnifications.

◯: ±10 μm.

Δ: ±20 μm.

X: ±25 μm.

As is apparent from the above results, the phosphor paste composition ofComparative Example 8 which did not contain 2-hydroxyethyl methacrylateat all gave a phosphor coating of poor smoothness and low patternaccuracy due to insufficient compatibility between the phosphor and thepolymer. When the proportion of 2-hydroxyethyl methacrylate exceeded 40%or the proportion of methacrylic acid, i.e., the unsaturated carboxylicacid exceeded 20%, the resulting phosphor paste composition had poorfiring characteristics. It is hence not preferable to contain them insuch great proportions respectively.

EXAMPLE 16

In 185 parts of diethylene glycol monobutyl ether acetate, 88 parts ofethyl methacrylate, 12 parts of 2-hydroxyethyl methacrylate and 2.0parts of BPO were reacted at 80° C. for 10 hours. An acrylic polymerthus obtained had a weight average molecular weight of 240,000.Dispersed in 100 solid parts of the thus-obtained acrylic polymer were450 parts of fine monochrome phosphor powder "P-45" of the same kind asthat employed in Example 1. The resultant mixture was kneaded and itsviscosity was adjusted with diethylene glycol monobutyl ether acetate to15,000 cps as measured at 25° C., thereby obtaining a phosphor pastecomposition. The composition obtained as described above was then coatedto a thickness of 20 μm on a glass plate by the screen printing process,followed by drying and firing. The surface of a phosphor coating thusobtained was evaluated. The surface of the phosphor coating wasevaluated by the optical microscope of 50-400 magnifications, using bothtransmitted light and reflected light. As a result, the surface of theresultant phosphor coating was found to contain no pinholes, to havehigh covering power and to present a smooth surface.

EXAMPLES 17-19 & COMPARATIVE EXAMPLES 11 AND 12

Phosphor paste compositions were separately prepared by changing, asshown in Table 6, the proportions of the acrylic polymer, which had beenobtained in Example 13, and a phosphor of the same kind as that employedin Example 12. The state of each printed coating was evaluated.

                  TABLE 6                                                         ______________________________________                                        Paste composition                                                             (parts)                                                                       Acrylic               150 μm       Firing                                  polymer (A)           pattern  smooth-                                                                              charac-                                 (solids)     Phosphor accuracy ness   teristics                               ______________________________________                                        Comp. 100        200      X      ◯                                                                        ◯                         Ex. 11                                                                        Ex. 17                                                                              100        450      ◯                                                                        ◯                                                                        ◯                         Ex. 18                                                                              100        600      ◯                                                                        ◯                                                                        ◯                         Ex. 19                                                                              100        1800     ◯                                                                        ◯-Δ                                                                ◯                         Comp. 100        2200     Δ-X                                                                            X      ◯                         Ex. 12                                                                        ______________________________________                                    

As is apparent from the above results, when the proportion of thephosphor was smaller than 250 parts per 100 solid parts of the acrylicpolymer, the resulting phosphor coating had poor pattern accuracy. Onthe other hand, when the phosphor content exceeded 2,000 parts, theresulting phosphor coating had not only poor smoothness but alsoundesirable pattern accuracy.

EXAMPLE 20

In 180 parts of 2,2,4-trimethyl-1,3-pentadiol monoisobutyrate, 84 partsof isobutyl methacrylate, 14 parts of 2-hydroxyethyl methacrylate, 2parts of methacrylic acid and 1.5 parts of kaya ester O (tert-butylperoctoate) were reacted at 80° C. for 10 hours. An acrylic polymer thusobtained had a weight average molecular weight of 260,000 and an acidvalue of 4.6. Dispersed in 100 solid parts of the acrylic polymer were380 parts of a color phosphor (P-22), which was of the same kind as thatemployed in Example 12, and 25 parts of fine silica powder. Theresultant mixture was kneaded and the viscosity was adjusted with2,2,4-trimethyl-1,3-pentadiol monoisobutyrate to 50,000 cps as measuredat 25° C., thereby obtaining a phosphor paste composition. The phosphorpaste composition obtained as described above was then coated in theform of stripes, which had a pattern width of 150 μm and a thickness of20 μm, on a glass plate by the screen printing process, followed bydrying and firing. The surface of a phosphor coating thus obtained wasevaluated. The surface of the phosphor coating was evaluated by theoptical microscope of 50-400 magnifications to evaluate the patternaccuracy and surface sate. As a result, the surface of the resultantphosphor coating was found to have a pattern accuracy of ±10 μm and topresent a smooth surface having no rough area.

EXAMPLES 21 AND 22 & COMPARATIVE EXAMPLES 13 AND 14

Printed coatings were separately formed in a similar manner as inExample 20 except that the viscosities of the corresponding pastes wereadjusted as shown in Table 7 by using 2,2,4-trimethyl-1,3-pentadiolmonoisobutyrate as a solvent. The state of each of the coatings wasevaluated in a similar manner as in Example 20.

                  TABLE 7                                                         ______________________________________                                               Viscosity                                                                             150 μm           Firing                                            of paste                                                                              pattern   Smooth-   charac-                                           (cps)   accuracy  ness      teristics                                  ______________________________________                                        Comp. Ex. 13                                                                            4000     X         ◯                                                                         ◯                            Ex. 20    8000     ◯-Δ                                                                   ◯                                                                         ◯                            Ex. 21   50000     ⊚                                                                        ◯                                                                         ◯                            Ex. 22   80000     ◯                                                                           ◯                                                                         ◯                            Comp. Ex. 14                                                                           240000    Δ-X X       ◯                            ______________________________________                                    

As is clearly envisaged from the above results, the coating printed atthe paste viscosity lower than 5,000 cps had insufficient patternaccuracy due to bleeding. On the other hand, the paste viscosity higherthan 200,000 resulted in a coating whose surface levelling was poor, sothat the surface was very rough and contained a marked trace of thescreen mesh and moreover the pattern accuracy was poor.

EXAMPLES 23 AND 24

Printed coatings were separately formed in a similar manner as inExample 20 except that the proportion of fine silica powder as athixotropic agent was changed as shown in Table 8. The state of each ofthe coatings was evaluated in a similar manner as in Example 20.

                  TABLE 8                                                         ______________________________________                                        Fine silica      150 μm pattern                                            powder (parts)   accuracy    Smoothness                                       ______________________________________                                        Ex. 23                                                                               0             ◯                                                                             ⊚                             Ex. 24                                                                              50             ⊚                                                                          ◯-Δ                        ______________________________________                                    

EXAMPLES 25 AND 26 & COMPARATIVE EXAMPLE 15 AND 16

Paste compositions were prepared in a similar manner as in Example 1except for the use of phosphor having different volume average particlesizes shown in Table 9. The state of a coating formed from each of thepaste compositions was evaluated in a similar manner as in Example 1.The results are also shown in Table 9.

                                      TABLE 9                                     __________________________________________________________________________    Volume average                                                                             Content of particles         Light-                              particle size                                                                              having a particle size                                                                   Pinholes    Aggregates                                                                          emitting                            of phosphor (μm)                                                                        greater than 6 μm (%)                                                                 in coating                                                                          Smoothness                                                                          (granules)                                                                          characteristics                     __________________________________________________________________________    Ex. 25                                                                            1.5       4         ◯                                                                       ◯                                                                       Δ                                                                             ◯                       Ex. 26                                                                            2.2       3         ⊚                                                                    ⊚                                                                    ◯                                                                       ◯                       Comp.                                                                             5.0      23         Δ                                                                             Δ                                                                             ◯                                                                       ◯                       Ex. 15                                                                        Comp.                                                                             8.0      30         X     X     ◯                                                                       ◯                       Ex. 16                                                                        __________________________________________________________________________

Aggregates

Each composition was printed, dried and fired. The surface of theresulting phosphor coating was evaluated by the optical microscope of 50magnifications.

◯: No phosphor aggregates of 30 μm and greater.

Δ: Some phosphor aggregates of 30 μm and greater.

X: Abundant phosphor aggregates of 30 μm and greater.

Light-Emitting Characteristics

Evaluation was made using as a standard a CRT manufactured by using thephosphor without grinding.

◯: Comparable with the standard.

X: Inferior to the standard.

COMPARATIVE EXAMPLES 17-19

Printed coatings were separately obtained in a similar manner as inExample 1 except that the fine phosphor powder having a volume averageparticle size of 8.0 μm was ground to the particle sizes given in Table10. The state of each of the coatings was evaluated. The results thusobtained are also shown in Table 10.

                  TABLE 10                                                        ______________________________________                                        Volume        Aggre-  Light-                                                  average par-  gates   emitting        Pinholes                                ticle size of (gran-  charac-  Smooth-                                                                              in                                      phosphor (μm)                                                                            ules)   teristics                                                                              ness   coating                                 ______________________________________                                        Comp. 0.7         X       X      ◯                                                                        ◯                         Ex. 17                                                                        Comp. 2.5         X       X      ◯                                                                        ◯                         Ex. 18                                                                        Comp. 5.0         Δ X      Δ-X                                                                            Δ                               Ex. 19                                                                        ______________________________________                                    

As is apparent from the results of Table 10, the use of the groundphosphors led to coatings of inferior light-emitting characteristics andof a state substantially equal to that available without grinding,although their particle sizes fell within the preferable range for thepresent invention.

EXAMPLES 27-30

Printed coatings were separately obtained in a similar manner as inExample 1 except that phosphors having the particle size distributioncharacteristics shown in Table 11 were used respectively. The state ofeach of the coatings was evaluated. The results thus obtained are alsoshown in Table 11.

                                      TABLE 11                                    __________________________________________________________________________    Particle size distribution                                                    of phosphor (con-  Volume  Pinholes        Light-                             tent in whole phosphor, %)                                                                       average particle                                                                      in   Smooth-                                                                            Aggregates                                                                          emitting                           <1     1-2                                                                              2-4                                                                              4-6                                                                              ≧6                                                                        size    coating                                                                            ness (granules)                                                                          characteristics                    __________________________________________________________________________    Ex. 27                                                                            15 30 50  5 0  2.4     ◯                                                                      ◯                                                                      Δ                                                                             ◯                      Ex. 28                                                                            5  25 60 10 0  3.2     ⊚                                                                   ⊚                                                                   ◯                                                                       ◯                      Ex. 29                                                                            1  19 75  5 0  3.0     ⊚                                                                   ⊚                                                                   ◯                                                                       ◯                      Ex. 30                                                                            5  15 30 35 15 3.8     ◯-Δ                                                              ◯-Δ                                                              ◯                                                                       ◯                      __________________________________________________________________________

EXAMPLES 31 AND 32 & COMPARATIVE EXAMPLES 20 AND 21

Printed coatings were separately obtained in a similar manner as inExample 12 except that phosphors having the particle sizecharacteristics shown in Table 12 were used respectively. The state ofeach of the coatings was evaluated. The results thus obtained are alsoshown in Table 12.

                                      TABLE 12                                    __________________________________________________________________________    Volume average                                                                             Content of particles having a                                    particle size                                                                              particle size greater than 9                                                                Pinholes    Aggregates                                                                          Light-emitting                                                                         150 μm               of phosphor (μm)                                                                        μm in phosphor (%)                                                                       in coating                                                                          Smoothness                                                                          (granules)                                                                          characteristics                                                                        pattern                 __________________________________________________________________________                                                          accuracy                Ex. 31                                                                            3.0       2            ◯                                                                       ◯                                                                       ◯                                                                       Δ  ◯           Ex. 32                                                                            4.5       7            ⊚                                                                    ⊚                                                                    ◯                                                                       ◯                                                                          ◯           Comp.                                                                             8.0      20            Δ-X                                                                           Δ                                                                             ◯                                                                       ◯                                                                          ◯           Ex. 20                                                                        Comp.                                                                             10.0     30            X     X     ◯                                                                       ◯                                                                          Δ                 Ex. 21                                                                        __________________________________________________________________________

COMPARATIVE EXAMPLES 22-24

Printed coatings were separately obtained in a similar manner as inExample 12 except that fine phosphor powder having the average particlesize of 7.6 μm was used after grinding it to the particle sizes shown inTable 13, respectively. The state of each of the coatings was evaluated.The results thus obtained are also shown in Table 13.

                  TABLE 13                                                        ______________________________________                                        Volume aver-  Aggre-  Light-                                                  age par-      gates   emitting        Pinholes                                ticle size of (gran-  charac-  Smooth-                                                                              in                                      phosphor (μm)                                                                            ules)   teristics                                                                              ness   coating                                 ______________________________________                                        Comp. 1.3         X       X      ◯                                                                        ◯                         Ex. 22                                                                        Comp. 3.0         X       X      ◯                                                                        ◯                         Ex. 23                                                                        Comp. 4.5         Δ X      ◯                                                                        ◯                         Ex. 24                                                                        ______________________________________                                    

As is clearly envisaged from the results of Table 13, the use of theground phosphors led to coatings of in inferior light-emittingcharacteristics and of a state substantially equal to that availablewithout grinding, although their particle sizes fell within thepreferable range for the present invention.

EXAMPLES 33-36

Printed coatings were separately obtained in a similar manner as inExample 12 except that phosphors having the particle size distributioncharacteristics shown in Table 14 were used respectively. The state ofeach of the coatings was evaluated. The results thus obtained are alsoshown in Table 14.

                                      TABLE 14                                    __________________________________________________________________________    Particle size distribution of phosphor                                                               Volume average                                                                         Pinholes        Light-  150                   (content in whole phosphor, %)                                                                       particle in   Smooth-                                                                            Aggregates                                                                          emitting                                                                              μm pattern         <1 μm                                                                              1-3                                                                              3-5                                                                              5-7                                                                              7-9                                                                              ≧9                                                                        size (μm)                                                                           coating                                                                            ness (granules)                                                                          characteristics                                                                       accuracy              __________________________________________________________________________    Ex. 33                                                                            2   25 58 13 2  0  3.5      ◯                                                                      ◯                                                                      Δ                                                                             ◯                                                                         ◯         Ex. 34                                                                            0   20 63 14 3  0  4.2      ⊚                                                                   ⊚                                                                   ◯                                                                       ◯                                                                         ◯         Ex. 35                                                                            0   22 71  7 0  0  4.5      ⊚                                                                   ⊚                                                                   ◯                                                                       ◯                                                                         ◯         Ex. 36                                                                            1   10 40 30 17 2  5.5      ◯-Δ                                                              ◯-Δ                                                              ◯                                                                       ◯                                                                         ◯         __________________________________________________________________________

The phosphor paste composition according to this invention has excellentfiring characteristics. Its use makes it possible to obtain a phosphorcoating having superb luminance and resolution and hence suited for aCRT. In addition, the phosphor paste composition uses a phosphor ofspecific particle size and particle size distribution. CRT manufacturedby using the phosphor paste composition is equipped with a substantiallypinhole-free phosphor coating which contains little roughness and hasexcellent light-emitting characteristics. The phosphor paste compositioncan therefore bring about enormous effects as a phosphor pastecomposition for a high-resolution CRT.

What is claimed is:
 1. A phosphor coating formed by printing a patternwith a phosphor paste composition containing an organic resin binder, anorganic solvent and a phosphor wholly surface-coated with a layer of anactivator, said phosphor having a volume average particle size in arange of 1-7 μm with particles having a particle size of 1-9 μmaccounting for at least 60 wt.%, and then firing the phosphor pastecomposition, to obtain a phosphor coating with no residue.
 2. Thephosphor coating as claimed in claim 1, wherein the phosphor is amonochrome phosphor having a volume average particle size of 1-4 μm. 3.The phosphor coating as claimed in claim 1, wherein the phosphor is acolor phosphor having a volume average particle size of 2-7 μm.